CN106241781B - The removing method of metal ion in graphite oxide - Google Patents
The removing method of metal ion in graphite oxide Download PDFInfo
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- CN106241781B CN106241781B CN201610580659.8A CN201610580659A CN106241781B CN 106241781 B CN106241781 B CN 106241781B CN 201610580659 A CN201610580659 A CN 201610580659A CN 106241781 B CN106241781 B CN 106241781B
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Abstract
The invention discloses metal ions in a kind of graphite oxide to remove method, and this method is first to prepare the acidic aqueous solution containing metal ion network mixture, is then washed to wherein concentration of metal ions graphite oxide lower than 10ppm with it；The preparation of acidic aqueous solution containing metal ion network mixture is under stirring, by with deionized water quality ratio in acidic aqueous solution is that 1:800~1:80 is added in acidic aqueous solution and stirs evenly by metal ion network mixture.Metal ion removes method in graphite oxide disclosed by the invention, and acidic aqueous solution provides acidic environment, to effectively inhibit the ionization of graphite oxide edge carboxylic acid ion；There is the metal ion network mixture of strong complexing simultaneously, capture the metal ion that carboxylate radical releases, have the function that rapidly remove wherein metal ion.
Description
Technical field
The invention belongs to graphite material impurity removing technology fields, and in particular to the removing side of metal ion in a kind of graphite oxide
Method.
Background technique
It 2004, is sent out by two scientist An Delie Jim of University of Manchester and Ke Siteyanuowoxiao love
Single-layer graphene now can be prepared using the method for tearing adhesive tape, and since acquisition Nobel Prize in physics in 2010, due to stone
The excellent mechanical property of black alkene and good thermal conductivity (5300W/mK), electric conductivity (15000cm2/ Vs) and translucency
(absorb 2.3% light) is considered being expected to be widely applied to new energy battery, sensor, computer, semiconductor etc. multiple
Field.
Currently, the method for preparing graphene has mechanical stripping method, oxidation-reduction method, SiC epitaxial growth method and chemical gaseous phase
Sedimentation (CVD), but only oxidation-reduction method can be realized large-scale production.And oxide-reduction method is to generally use permanganic acid
Potassium, potassium ferrate, potassium hyperchlorate etc. first carry out graphite to aoxidize obtained graphite oxide as oxidant, then by ultrasound or
The methods of mechanical shock removes graphite oxide to obtain graphene oxide, reuses the change that hydrazine hydrate etc. has reduction
Substance, which carries out reduction to graphene oxide, can be obtained graphene.Wherein, common method for oxidation is by improved
Hummer ' s method prepares graphite oxide, and improved hummer ' s method be traditional hummer ' s method (Hummers,
W.S.&Offeman,R.E.Preparation of graphitic oxide.J.Am.Chem.Soc.80,1339–1339
(1958)) on the basis of, the proportion of oxidizing temperature, oxidization time and graphite and potassium permanganate is improved to obtain oxidation stone
Ink.Due to metal ion (such as the Mn during graphite oxidation because using oxidant to introduce2+、Fe2+), it will receive graphite oxide
Carboxylic acid ion strong complexing in alkene edge causes to be difficult to be washed away in water-washing process later.And metal ion
There are problems that being easy to produce following several respects: (1) due to the complexing of metal ion, so that graphene oxide electrostatic interaction
Power weakens, and then influences the removing of graphite oxide；(2) it is easy to produce in graphene edge since metal oxide itself is non-conductive
Raw defect, to influence the mechanical property and electric property in graphene use process；(3) since graphene is expected to be used for wear
The manufacture (such as Flexible graphene mobile phone) of wearing electronic product, meeting and direct physical contact seriously threaten biological health, and work as
When the electronic product for containing graphene is abandoned as electronic waste, there is also the potential hazards of pollution environment.
The metal ion as present in graphite oxide can generate the above problem, and the application of graphene is caused greatly to be limited
System.How quickly to remove a small amount of metal ion present in graphite oxide and becomes a technical problem in the urgent need to address.
Summary of the invention
The purpose of the present invention is intended to for above-mentioned problems of the prior art, provide in a kind of graphite oxide metal from
The removing method of son keeps the removing of graphite oxide suitable can quickly and effectively remove metal ion present in graphite oxide
Benefit carries out, and further increases the mechanical property and electric property of graphene.
To achieve the goals above, the present invention takes following technical scheme to realize.
The present invention provides a kind of removing method of metal ion in graphite oxide, this method be first prepare containing metal from
Then the acidic aqueous solution of sub- complexing agent washs to wherein concentration of metal ions lower than 10ppm graphite oxide with it, then
It is washed with deionized water to solution and is in neutrality.
The preparation of the acidic aqueous solution containing metal ion network mixture is to stir in the removing method of above-mentioned metal ion
Under state, metal ion network mixture is added to acidity by with deionized water quality ratio in acidic aqueous solution for 1:800~1:80
It is stirred evenly in aqueous solution.Herein, the complexing of the metal ion network mixture of selection must be better than carboxylic acid ion,
To can just capture the metal ion that carboxylate radical releases, have the function that rapidly remove wherein metal ion.Therefore, do not drawing
Under the premise of entering other foreign ions, metal ion network mixture still has very wide selectable range, can be alcamines
Close at least one of object, aminocarboxylate, organic phosphate, phosphate and polyacrylic compounds.Wherein, alcamines
Closing object can be monoethanolamine, diethanol amine, triethanolamine etc.；Aminocarboxylate can be sodium ammonium triacetate (NTA), ethylenediamine
Tetraacetate (EDETATE SODIUM or four sodium), diethylenetriamine pentacarboxylic acid salt (DTPA) etc.；Organic phosphate can be phytic acid, second two
Four methene sodium phosphate (EDTMPS) of amine, diethylene triamine pentamethylene phosphonic salt (DETPMPS), three methene phosphate of amine etc.；Phosphoric acid
Salt can be sodium phosphate, potassium phosphate etc.；Polyacrylic compounds can be hydrolysis of polymaleic anhydride (HPMA), polyacrylic acid
(PAA), poly- hydroxy acrylic acid, maleic acrylic copolymer and polyacrylamide etc..Due to metal in graphite oxide itself
Ion concentration is not high, and when metal ion network mixture excessive concentration in acidic aqueous solution, it undoubtedly will increase production cost, pass through
Cross the study found that when in metal ion network mixture and acidic aqueous solution deionized water quality ratio be that 1:800~1:80 can be with
Meet the requirement that the present invention removes metal ion in graphite oxide；When deionization in metal ion network mixture and acidic aqueous solution
When water quality ratio is greater than 1:200, although can be by increasing cleaning solution dosage mode, metal ion be gone in raising graphite oxide
Except rate, but the waste of cleaning solution can be still caused to a certain extent in this way, when metal ion complexing agent and acidic aqueous solution
When middle deionized water quality ratio is 1:200~1:80, the requirement that the present invention removes metal ion in graphite oxide both can satisfy,
It can also be further reduced the dosage of cleaning solution simultaneously, reduce the wasting of resources, reduce cost.
The pH value of prepared acidic aqueous solution is 1~6 in the removing method of above-mentioned metal ion.Acidic aqueous solution can be with
It directlys adopt deionized water and acid is diluted to obtain.The acid of above-mentioned preparation acidic aqueous solution is in hydrochloric acid, sulfuric acid and nitric acid
It is at least one.Herein, since the effect of acidic aqueous solution is to provide acidic environment, effectively to inhibit graphite oxide edge carboxylic acid
The ionization of radical ion, therefore other than the selection of above-mentioned conventional acid, under the premise of not introducing other foreign ions, it can also adopt
The aqueous solution of acidic environment can be provided with other.
Concentration of metal ions can not only be made to be reduced to 8.33ppm in graphite oxide using method provided by the invention hereinafter,
And if the preferred edetate of metal ion network mixture (EDETATE SODIUM or four sodium), can also under the above conditions,
Make the concentration of metal ions after washing in graphite oxide lower than 1ppm, reaches 0.85ppm or less.At this moment it is considered that graphite oxide
In metal ion removed substantially it is clean.
In addition, if graphite oxide is obtained using improved hummer ' s method, it is a large amount of due to having been used when preparation
The concentrated sulfuric acid, can also make the acidity in graphite oxide excessively high, at this time if by needing to prepare containing metal ion network mixture
If acidic aqueous solution pH sets relatively higher (such as pH value limit on the upper side), such as preferably 3~6, the use of acid on the one hand can be reduced in this way
Amount reduces cost, on the other hand can also carry out pickling while removing metal ion to graphite oxide with killing two birds with one stone, save
Go the difficulty of conventional pickling process or reduction pickling process.
The removing method of above-mentioned metal ion is to pass through routine using the acidic aqueous solution containing metal ion network mixture
What centrifugation or natural sedimentation washed graphite oxide, washing times are generally 1-5 times, from removing metal ion effect
Consider that washing times are preferably 3-5 times.
The removing method of metal ion, has the advantages that in graphite oxide provided by the invention
1, since the removal of impurities aqueous solution that the method for the present invention uses can not only provide acidic environment, also containing strong complexing
Metal ion network mixture, thus can effectively inhibit the ionization of graphite oxide edge carboxylic acid ion and capture carboxylate radical
The metal ion released achievees the purpose that rapidly remove wherein metal ion.
2, the metal ion in graphite oxide can be removed due to the method for the present invention, thus can make the carboxylic acid in graphite oxide
Root is in complete ionized state, increases electrostatic interaction between lamella, so that graphite oxide is easier to be stripped to obtain in the later period
Graphene oxide.
3, it can be handled by centrifugation due to the method for the present invention, it is thus possible to accelerate graphite oxide in solution
The rate of settling, improve graphite oxide in metal ion removal efficiency.
4, it since the method for the present invention is that the acid water containing metal ion network mixture washs graphite oxide, not only can remove
Metal ion in graphite oxide, while also there is preferable pickling effect, and opposite conventional oxidation graphene preparation process
It is middle carry out pickling amount (every each washing needs water 1000mL of g graphite oxide) with water for, when be applied to industrialized production when,
Water consumption can greatly reduce, and while saving water resource, decrease the pollution to water resource, reduce sewage load.
5, due between the of the invention metal ion network mixture chosen and graphite oxide there is no interaction, because without
Introduce new impurity.
6, after the metal ion in graphite oxide can be removed due to the method for the present invention, thus it can be further improved reduction
Obtained graphene purity reduces bio-toxicity and the pollution generated to environment that metal ion is brought.
Detailed description of the invention
In order to illustrate the embodiments of the present invention more clearly with the difference of technical solution in the prior art, below to embodiment
Or attached drawing needed to be used in the description of the prior art is briefly described, it should be apparent that, be described below in attached drawing only
It is some embodiments of the present invention, for those of ordinary skills, without creative efforts, also
Illustrated embodiment other embodiments and its attached drawing can be obtained according to these attached drawings, but protection scope of the present invention should be included in
It is interior.
Fig. 1 is shown the embodiment of the present invention 1 (a), embodiment 2 (b), comparative example 1 (e) and comparative example 2 (d) and is washed using difference
Liquid is to Mn in graphite oxide washing process2+Wash-off amount is used with the variation histogram of wash number, comparative example 3 (c) contains metal
The acidic aqueous solution of ionic complexing agent is to Mn in the graphene oxide washing process after graphite oxide removing2+Wash-off amount is with cleaning time
Mn in several variation histograms and respective final product2+Content histogram.
Fig. 2 shows the embodiment of the present invention 1 (a), embodiment 2 (b), comparative example 1 (e), comparative example 2 (d) and comparative examples 3
(c) histogram that S content changes with washing lotion type in final product.
Fig. 3 shows the final product of the embodiment of the present invention 1 (a), embodiment 2 (b), embodiment 3 (f) and embodiment 4 (g)
Middle Mn2+The histogram that content changes with metal ion network mixture type.
Fig. 4 shows Mn in the final product of the embodiment of the present invention 6 (h), embodiment 7 (i) and embodiment 8 (j)2+Content with
The histogram of metal ion network mixture and deionized water proportion variation in washing lotion.
Fig. 5 shows the embodiment of the present invention 6 (h), embodiment 7 (i), embodiment 8 (j) and graphite oxide in embodiment 9 (k)
The histogram that washing lotion pH value changes with washing times after washing.
Specific embodiment
Clear, complete description is carried out below with reference to technical solution of the attached drawing to various embodiments of the present invention, it is clear that is retouched
Stating embodiment is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, originally
Field those of ordinary skill obtained all other embodiment without making creative work, belongs to this hair
Bright protected range.
The content of manganese ion is using ICP in oxidation graphite solid given by following embodiment and comparative example
(Inductively coupled plasma, inductively coupled plasma body) test.
Embodiment 1
The graphite oxide that the present embodiment uses is obtained by following preparation method: in 0 DEG C~15 DEG C ice-water baths, by 1g stone
It is under stirring, to divide 6 times in 1h and 3g high is added altogether in 95~98% concentrated sulfuric acids that ink, which is added and fills 100mL mass concentration,
Potassium manganate continues to stir 1h in ice-water bath after adding, temperature is then risen to 35 DEG C, keep 2h, 215mL deionization is added
Water, then temperature is risen to 98 DEG C maintains to sequentially add after 1h hydrogen peroxide that 200mL deionized water and mass concentration are 30% to molten
Liquid bubble-free generates, and filters and completes to obtain graphite oxide.
Then the acidic aqueous solution for being first 3 with hydrochloric acid and deionized water secure ph is pressed EDETATE SODIUM and deionized water
Mass ratio is added in acidic aqueous solution for 1:200 to stir evenly；Obtained graphite oxide is taken, it is prepared by taking every time
800mL acidic aqueous solution, centrifuge washing 10min removes supernatant, repeated washing totally three under the conditions of revolving speed is 3000r/min
It is secondary；800mL deionized water is used again, centrifuge washing 10min under the conditions of revolving speed is 3000r/min, after removing supernatant, by gained
Graphite oxide is added in 800ml deionized water dispersion and freeze-dried obtains oxidation graphite solid.
It is tested through ICP, the content of manganese ion is 0.74889ppm in the oxidation graphite solid.
Embodiment 2
The graphite oxide preparation method that the present embodiment uses is same as Example 1, slightly.
It is in mass ratio first acidic aqueous solution that 1:500 prepares that pH is 1.6 with phytic acid and deionized water；Take obtained oxygen
Graphite is centrifuged in 10min removal under the conditions of revolving speed is 3000r/min by prepared 800mL acidic aqueous solution is taken every time
Clear liquid, repeated washing are total three times；800mL deionized water is used again, and centrifuge washing 10min under the conditions of revolving speed is 3000r/min is gone
After supernatant, gained graphite oxide is added to dispersion in 800ml deionized water and the freeze-dried graphite oxide that obtains is consolidated
Body.
It is tested through ICP, the content of manganese ion is 4.7449ppm in the oxidation graphite solid.
Embodiment 3
The graphite oxide preparation method that the present embodiment uses is same as Example 1, slightly.
Then the acidic aqueous solution for being first 3 with nitric acid and deionized water secure ph is pressed sodium phosphate and deionized water
Amount is stirred evenly than being added in pickling aqueous solution for 1:500；Obtained graphite oxide is taken, it is prepared by taking every time
800mL acidic aqueous solution, centrifuge washing 10min removes supernatant, repeated washing totally three under the conditions of revolving speed is 3000r/min
It is secondary, then with 800mL deionized water, centrifuge washing 10min under the conditions of revolving speed is 3000r/min, after removing supernatant, by gained
Graphite oxide is added in 800ml deionized water dispersion and freeze-dried obtains oxidation graphite solid.
It is tested through ICP, the content of manganese ion is 8.326ppm in the oxidation graphite solid.
Embodiment 4
The graphite oxide preparation method that the present embodiment uses is same as Example 1, slightly.
Then the acidic aqueous solution for being first 3 with hydrochloric acid and deionized water secure ph is pressed diethanol amine and deionized water
Mass ratio is added in acidic aqueous solution for 1:500 to stir evenly；Obtained graphite oxide is taken, it is prepared by taking every time
800mL acidic aqueous solution, centrifuge washing 10min removes supernatant, repeated washing totally three under the conditions of revolving speed is 3000r/min
It is secondary；800mL deionized water is used again, centrifuge washing 10min under the conditions of revolving speed is 3000r/min, after removing supernatant, by gained
Graphite oxide is added in 800ml deionized water dispersion and freeze-dried obtains oxidation graphite solid.
It is tested through ICP, the content of manganese ion is 6.269ppm in the oxidation graphite solid.
Embodiment 5
The graphite oxide preparation method that the present embodiment uses is same as Example 1, slightly.
Then the acidic aqueous solution for being first 3 with nitric acid and deionized water secure ph is pressed polyacrylic acid and deionized water
Mass ratio is added in pickling aqueous solution for 1:800 to stir evenly；Obtained graphite oxide is taken, it is prepared by taking every time
800mL acidic aqueous solution, centrifuge washing 10min removes supernatant, repeated washing totally three under the conditions of revolving speed is 3000r/min
It is secondary；800mL deionized water is used again, centrifuge washing 10min under the conditions of revolving speed is 3000r/min, after removing supernatant, by gained
Graphite oxide is added in 800ml deionized water dispersion and freeze-dried obtains oxidation graphite solid.
It is tested through ICP, the content of manganese ion is 8.234ppm in the graphite oxide.
Embodiment 6
The graphite oxide preparation method that the present embodiment uses is same as Example 1, slightly.
Then the acidic aqueous solution for being first 6 with hydrochloric acid and deionized water secure ph is pressed EDETATE SODIUM and deionized water
Mass ratio is added in acidic aqueous solution for 1:80 to stir evenly；Obtained graphite oxide is taken, it is prepared by taking every time
800mL acidic aqueous solution, centrifuge washing 10min removes supernatant, repeated washing totally three under the conditions of revolving speed is 3000r/min
It is secondary；800mL deionized water is used again, centrifuge washing 10min under the conditions of revolving speed is 3000r/min, after removing supernatant, by gained
Graphite oxide is added in 800ml deionized water dispersion and freeze-dried obtains oxidation graphite solid.
It is tested through ICP, the content of manganese ion is 0.6549ppm in the oxidation graphite solid.
Embodiment 7
The graphite oxide preparation method that the present embodiment uses is same as Example 1, slightly.
Then the acidic aqueous solution for being first 6 with sulfuric acid and deionized water secure ph is pressed EDETATE SODIUM and deionized water
Mass ratio is added in acidic aqueous solution for 1:200 to stir evenly；Obtained graphite oxide is taken, it is prepared by taking every time
100mL acidic aqueous solution, centrifuge washing 10min removes supernatant, repeated washing totally three under the conditions of revolving speed is 3000r/min
It is secondary；800mL deionized water is used again, centrifuge washing 10min under the conditions of revolving speed is 3000r/min, after removing supernatant, by gained
Graphite oxide is added in 100ml deionized water dispersion and freeze-dried obtains oxidation graphite solid.
It is tested through ICP, the content of manganese ion is 0.7267ppm in the oxidation graphite solid.
Embodiment 8
The graphite oxide preparation method that the present embodiment uses is same as Example 1, slightly.
Then the acidic aqueous solution for being first 6 with sulfuric acid and deionized water secure ph is pressed EDETATE SODIUM and deionized water
Mass ratio is added in acidic aqueous solution for 1:800 to stir evenly；Obtained graphite oxide is taken, it is prepared by taking every time
3200mL acidic aqueous solution, centrifuge washing 10min removes supernatant, repeated washing totally three under the conditions of revolving speed is 3000r/min
It is secondary；It is washed again with 3200mL deionized water, centrifuge washing 10min under the conditions of revolving speed is 3000r/min, after removing supernatant,
Gained graphite oxide is added in 3200ml deionized water dispersion and freeze-dried obtains oxidation graphite solid.
It is tested through ICP, the content of manganese ion is 53.289ppm in the oxidation graphite solid.
Embodiment 9
The graphite oxide preparation method that the present embodiment uses is same as Example 1, slightly.
Then the acidic aqueous solution for being first 6 with sulfuric acid and deionized water secure ph is pressed EDETATE SODIUM and deionized water
Mass ratio 1:800, which is added in acidic aqueous solution, to stir evenly；Obtained graphite oxide is taken, it is prepared by taking every time
5000mL acidic aqueous solution, centrifuge washing 10min removes supernatant, repeated washing totally three under the conditions of revolving speed is 3000r/min
It is secondary；3200mL deionized water is used again, centrifuge washing 10min under the conditions of revolving speed is 3000r/min, after removing supernatant, will
To graphite oxide be added in 5000ml deionized water dispersion and freeze-dried obtain oxidation graphite solid.
It is tested through ICP, the content of manganese ion is 0.8453ppm in the graphite oxide.
Embodiment 10
The graphite oxide preparation method that the present embodiment uses is same as Example 1, slightly.
Then the acidic aqueous solution for being first 3 with hydrochloric acid and deionized water secure ph is pressed tetra- sodium of EDTA and deionized water
Mass ratio 1:200, which is added in acidic aqueous solution, to stir evenly；Obtained graphite oxide is taken, it is prepared by taking every time
800mL acidic aqueous solution, centrifuge washing 10min removes supernatant, repeated washing totally five under the conditions of revolving speed is 3000r/min
It is secondary；800mL deionized water is used again, and centrifuge washing 10min under the conditions of revolving speed is 3000r/min will be obtained after removing supernatant
Graphite oxide be added in 800ml deionized water dispersion and freeze-dried obtain oxidation graphite solid.
It is tested through ICP, the content of manganese ion is 0.6534ppm in the graphite oxide.
Embodiment 11
The graphite oxide preparation method that the present embodiment uses is same as Example 1, slightly.
Then the acidic aqueous solution for being first 4 with hydrochloric acid and deionized water secure ph is pressed tetra- sodium of EDTA and deionized water
Mass ratio 1:200, which is added in acidic aqueous solution, to stir evenly；Obtained graphite oxide is taken, it is prepared by taking every time
800mL acidic aqueous solution, centrifuge washing 10min removes supernatant, repeated washing totally three under the conditions of revolving speed is 3000r/min
It is secondary；800mL deionized water is used again, and centrifuge washing 10min under the conditions of revolving speed is 3000r/min will be obtained after removing supernatant
Graphite oxide be added in 800ml deionized water dispersion and freeze-dried obtain oxidation graphite solid.
It is tested through ICP, the content of manganese ion is 0.7543ppm in the graphite oxide.
Embodiment 12
The graphite oxide preparation method that the present embodiment uses is same as Example 1, slightly.
Then the acidic aqueous solution for being first 3 with hydrochloric acid and deionized water secure ph is pressed EDETATE SODIUM and deionized water
Mass ratio 1:150, which is added in acidic aqueous solution, to stir evenly；Obtained graphite oxide is taken, it is prepared by taking every time
800mL acidic aqueous solution, centrifuge washing 10min removes supernatant, repeated washing totally three under the conditions of revolving speed is 3000r/min
It is secondary；800mL deionized water is used again, and centrifuge washing 10min under the conditions of revolving speed is 3000r/min will be obtained after removing supernatant
Graphite oxide be added in 800ml deionized water dispersion and freeze-dried obtain oxidation graphite solid.
It is tested through ICP, the content of manganese ion is 0.7943ppm in the graphite oxide.
Comparative example 1
The graphite oxide preparation method that this comparative example uses is same as Example 1, slightly.
Using deionized water as washing lotion, obtained graphite oxide is taken, by 800mL deionized water is taken every time, is in revolving speed
Centrifuge washing 10min abandons supernatant under the conditions of 3000r/min, washes repeatedly totally four times；Gained graphite oxide is added to 800ml
Dispersion and freeze-dried oxidation graphite solid is obtained in deionized water.
It is tested through ICP, the content of manganese ion is 567.34ppm in the oxidation graphite solid.
Comparative example 2
The graphite oxide preparation method that this comparative example uses is same as Example 1, slightly.
The acidic aqueous solution for being first 3 with hydrochloric acid and deionized water secure ph；Obtained graphite oxide is taken, by taking every time
Prepared 800mL acidic aqueous solution, centrifuge washing 10min removes supernatant under the conditions of revolving speed is 3000r/min, and repetition is washed
It washs altogether three times；800mL deionized water is used again, centrifuge washing 10min under the conditions of revolving speed is 3000r/min, after removing supernatant,
Gained graphite oxide is added in 800ml deionized water dispersion and freeze-dried obtains oxidation graphite solid.
It is tested through ICP, the content of manganese ion is 612.85ppm in the oxidation graphite solid.
Comparative example 3
The graphite oxide preparation method that this comparative example uses is same as Example 1, slightly.
Then the acidic aqueous solution for being first 3 with hydrochloric acid and deionized water secure ph is pressed EDETATE SODIUM and deionized water
Mass ratio 1:200, which is added in acidic aqueous solution, to stir evenly；Obtained graphite oxide is taken to use under the conditions of power is 300W
Ultrasonic machine ultrasound 10min removes to obtain graphene oxide；Again to obtained graphene oxide, by taking prepared 800mL every time
Acidic aqueous solution, centrifuge washing 10min removes supernatant under the conditions of revolving speed is 3000r/min, and repeated washing is total three times；It uses again
Gained is aoxidized stone after removing supernatant by 800mL deionized water, centrifuge washing 10min under the conditions of revolving speed is 3000r/min
Black alkene is added in 800ml deionized water dispersion and freeze-dried obtains graphene oxide solid.
It is tested through ICP, the content of manganese ion is 7.41848ppm in the graphene oxide.
In order to probe into the present invention provide graphite oxide in the metal ion method of going out feasibility, the present invention to embodiment 1,
In 1 to 3 cleaning process of embodiment 2 and comparative example, Mn in solid product2+Wash-off amount is with the situation of change of wash number and final
Mn in product2+Content and S content are analyzed, and analysis result is as shown in Figures 1 and 2.It will be seen from figure 1 that using EDTA bis-
The aqueous solution of the acidic aqueous solution of sodium or phytic acid washs graphite oxide, with wash number, the Mn that washes out every time2+Amount is gradually
It reduces, Mn in final product2+Content is respectively less than 10ppm；And acidic aqueous solution or deionized water is used to wash graphite oxide,
The Mn washed out every time2+Measure substantially similar, Mn in final product2+Content is still higher than 500ppm, illustrates the Mn washed out2+Seldom.
It can be seen that the metal ion in graphite oxide can be effectively removed using the acidic aqueous solution containing metal ion network mixture.
Meanwhile graphite oxide is washed using the acidic aqueous solution containing metal ion network mixture as can be seen from Figure 2, equally to washing oxygen
Sulfate ion in graphite also has very good effect.
Although in addition, water-soluble after being removed graphite oxide to obtain graphene oxide, then with the acidity containing EDTA
Liquid washs graphene oxide, removes Mn2+Effect be also also possible that Mn in final product2+Content reaches 7.41848ppm；But it ties
Closing Fig. 2 can be seen that using the graphene oxide after removing since huge specific surface area can adsorb more sulfuric acid, cause
The residual volume of element sulphur is significantly larger than other using graphite oxide, so using the acidic aqueous solution of metal ion complexing agent
It is unreasonable to wash graphene oxide.
In order to probe into the function and effect of various metal ion network mixture, the present invention is to 4 final product of embodiment 1- embodiment
Middle Mn2+Content is analyzed, as a result as shown in Figure 3；It can be seen from the figure that containing EDTA in various metal ion network mixture
The acidic aqueous solution of disodium is to Mn2+Wash out efficiency highest.Due to being all amino and carboxyl in aminocarboxylate structure, by this two
Kind group plays complexing, so all aminocarboxylates are removing deoxidation as the acidic aqueous solution that metal ion network mixture is prepared
In graphite in terms of metal ion, there is effect similar with EDETATE SODIUM.
In order to probe into metal ion network mixture and deionized water quality than the shadow in graphite oxide in metal ion removal
It rings, the present invention is to Mn in 8 final product of embodiment 6- embodiment2+Content is analyzed, as a result as shown in Figure 4；It can be with from figure
Find out, when metal ion network mixture EDETATE SODIUM and deionized water quality ratio are 1:80 and 1:200, in graphite oxide metal from
The wash-off efficiency of son is fairly obvious；And when EDETATE SODIUM and deionized water quality ratio are less than 1:800, due to acid water-soluble
EDETATE SODIUM concentration is too small in liquid, such acidic aqueous solution its remove metal ion the effect is unsatisfactory.
In order to probe into the acid-base property after graphite oxide washing, to the pH of the washing lotion of embodiment 6- embodiment 9 each time after washing
Value is tested and analyzed, and testing result is as shown in Figure 5.From fig. 5, it can be seen that with the increase of washing times, graphite oxide is washed
The pH value for washing rear washing lotion is gradually increased, after the washing of acidic aqueous solution three times and a deionized water washing, the pH of washing lotion
Value has been approached neutrality.For embodiment 6, each washing lotion dosage is 800mL, and after four washings, pickling goes out to imitate in graphite oxide
Rate is very high, even if being further added by each washing lotion dosage (see embodiment 8,9), washed out efficiency change is not fairly obvious.It is right
In embodiment 7, each washing lotion dosage is 100mL, after the washing of acidic aqueous solution three times and a deionized water washing, although
Metal ion is effectively removed, but the pH value of the washing lotion after four washings is still lower, in order to meet the application of graphite oxide
Demand, it is still necessary to continue to be washed with deionized to neutrality.It can thus be seen that when the graphite oxide of processing 1g graphite preparation
When, each washing lotion dosage should be controlled in 100~800mL.
Those of ordinary skill in the art will understand that embodiment here be to help reader understand it is of the invention
Principle, it should be understood that protection scope of the present invention is not limited to such specific embodiments and embodiments.This field it is common
Technical staff disclosed the technical disclosures can make the various various other tools for not departing from essence of the invention according to the present invention
Body variations and combinations, these variations and combinations are still within the scope of the present invention.
Claims (3)
1. a kind of removing method of metal ion in graphite oxide, it is characterised in that this method is first to prepare to contain metal ion network
Then the acidic aqueous solution of mixture washs to wherein manganese ion concentration lower than 1ppm graphite oxide with it；It prepares acid
The acid of aqueous solution is at least one of hydrochloric acid, sulfuric acid and nitric acid；In the acidic aqueous solution containing metal ion network mixture
Metal ion network mixture is edetate；Metal ion network mixture in acidic aqueous solution containing metal ion network mixture
It is 1:200~1:80 with deionized water quality ratio in acidic aqueous solution.
2. the removing method of metal ion in graphite oxide according to claim 1, it is characterised in that this method is prepared
Acidic aqueous solution pH value be 1~6.
3. the removing method of metal ion in graphite oxide according to claim 1 or 2, it is characterised in that this method is with containing
Having the acidic aqueous solution of metal ion network mixture is 1~5 time to graphene oxide washing times.
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| CN108793134B (en) * | 2018-08-07 | 2022-02-22 | 中山市悦泰汽车零部件有限公司 | Preparation method of graphene |
| CN109502580B (en) * | 2018-12-07 | 2021-01-22 | 四川聚创石墨烯科技有限公司 | Purification device of graphene oxide |
| CN109292767B (en) * | 2018-12-07 | 2021-05-04 | 四川聚创石墨烯科技有限公司 | Purification method of graphene oxide |
| CN109319773B (en) * | 2018-12-07 | 2021-03-19 | 四川聚创石墨烯科技有限公司 | Comprehensive treatment method of graphene oxide slurry |
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| CN104787759A (en) * | 2015-04-20 | 2015-07-22 | 德阳烯碳科技有限公司 | Impurity removal method in preparation process of graphene |
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| CN111249765A (en) * | 2020-02-25 | 2020-06-09 | 中国科学院化学研究所 | Pressurized fluid extraction system and method for removing metal ions from carbon material |
| CN111249765B (en) * | 2020-02-25 | 2021-04-06 | 中国科学院化学研究所 | Pressurized fluid extraction system and method for removing metal ions from carbon material |
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